Arsenic sequestration by sorption processes in high-iron sediments

High-iron sediments in North Haiwee Reservoir (Olancha, CA), resulting from water treatment for removal of elevated dissolved arsenic in the Los Angeles Aqueduct system, were studied to examine arsenic partitioning between solid phases and porewaters undergoing shallow burial. To reduce arsenic in drinking water supplies, ferric chloride and a cationic polymer coagulant are added to the aqueduct upstream of Haiwee Reservoir, forming an iron-rich floc that scavenges arsenic from the water. Analysis by synchrotron X-ray absorption spectroscopy (XAS) showed that the aqueduct precipitate is an amorphous hydrous ferric oxide (HFO) similar to ferrihydrite, and that arsenic is associated with the floc as adsorbed and/or coprecipitated As(V). Arsenic-rich floc and sediments are deposited along the inlet channel as aqueduct waters enter the reservoir. Sediment core samples were collected in two consecutive years from the edge of the reservoir along the inlet channel using 30- or 90-cm push cores. Cores were analyzed for total and extractable arsenic and iron concentrations. Arsenic and iron speciation and mineralogy in sediments were examined at selected depths by synchrotron XAS and X-ray diffraction (XRD). Sediment-porewater measurements were made adjacent to the core sample sites using polyacrylamide gel probe samplers. Results showed that sediment As(V) is reduced to As(III) in all cores at or near the sediment-water interface (0-4 cm), and only As(III) was observed in deeper sediments. Analyses of EXAFS spectra indicated that arsenic is present in the sediments mostly as a bidentate-binuclear, inner-sphere sorption complex with local atomic geometries similar to those found in laboratory studies. Below about 10 cm depth, XAS indicated that the HFO floc had been reduced to a mixed Fe(II, III) solid with a local structure similar to that of synthetic green rust (GR) but with a slightly contracted average interatomic Fe-Fe distance in the hydroxide layer. There was no evidence from XRD for the formation of a crystalline GR phase. The release of dissolved iron (presumably Fe2+) and arsenic to solution, as monitored by in situ gel probes, was variable but, in general, occurred at greater depths than arsenic reduction in the sediments by spectroscopic observations and appears to be near or below the depth at which sediment GR was identified. These data point to reductive dissolution of the sorbent iron phase as the primary mechanism of release of sorbed arsenic to solution. © 2007 Elsevier Ltd. All rights reserved.

Fate of volatile fluorinated compounds in the subsurface

Christian Balsiger

Since their discovery around 1930, the synthetic compounds of the class of chlorofluorocarbons (CFCs) have been produced and used worldwide at very large scale. Their physico-chemical properties (non-flammability, chemical inertia, miscibility with water and oil, compatibility with many metals and plastics, solvent capacity) have made them ideal candidates for several applications, such as refrigerant fluids, aerosol propellants, foam blowing agents, or as solvents or intermediates of chemical synthesis. In the 70', it was demonstrated that following their release in the atmosphere, they are implicated in the process leading to the commonly called stratospheric ozone hole. The governments of several industrialised country have thus signed a protocol with the objective to stop the production and use of CFCs. CFCs have been increasingly replaced by compounds with similar structure, the hydrochlorofluorocarbons (HCFCs), but whose reactivity in the lower layers of the atmosphere is quite different from that of CFCs. Due to their chemical inertia, CFCs has been used as tracers for surface and groundwater datation. During such investigations, the biodegradability of these compounds and the existence of punctual pollution sources in soil and groundwater have been evidenced. It has been demonstrated that some of these compounds can be dechlorinated under anoxic conditions producing other compounds with sometimes higher toxicity and higher water solubility, and resulting in a risk linked to the consumption of natural groundwater. The goal of this thesis was to get indications about reductive transformations of CFCs and especially HCFCs in Swiss aquifers and landfills, on the potential of different microbial communities to reductively dechlorinate certain compounds, and under which redox conditions the transformations occur in aquifer systems. Data concerning the production, use, emission, regulation, as well as the biodegradability and toxicity of these compounds are presented in chapter 1 and in the appendix. The analytical methods developed and used during this work are presented in chapter 2. Particularly, a versatile analytical system allowing the measure of trace but also higher concentrations in different media, solid or aqueous, has been set up and used during this work. CFCs and HCFCs were analyzed at 3 sites in Switzerland. Samples were collected from a natural groundwater in which a chloroethene plume had been observed, from an old landfill closed in 1980, and from a more recent bioactive landfill constructed in horizontal layers. In addition, the behaviour of different CFCs and HCFCs was studied in microcosms inoculated with sludge originating from several sewage treatment plants in the canton of Vaud, and with a sediment originating from a contaminated aquifer in Holland. The studied CFCs and HCFCs were furthermore injected at the inlet of a 1.2 m height column filled with the aquifer sediment from Holland. In this quasi natural aquifer, the oxido-reductive conditions were modified during the experiment in order to investigate the conditions at which the biodegradation occurred. The field studies showed that CFCs and HCFCs are present in aquifers and landfills, and there were indications that their transformation also occurs there. Estimations of half-life times indicated that the reductive dechlorination occurred at slow rates. This could be due to the low temperatures of natural groundwater systems and other factors linked to the hydro-geological properties of the natural environment such as dispersion, sorption or partitionning. In the microcosms inoculated with sludge, CFC-11 was transformed to HCFC-21, the latter being further dechlorinated to HCFC-31. HCFC-123a and chlorotrifluoroethene (CTFE) were produced simultaneously from CFC-113. Inhibition of methanogesis with 2 bromoethane sulfonate decreased significantly the degradation rate of CFC-11, emphasizing the importance of the role of methanogens in the degradation process. In the microcosms inoculated with the contaminated sediment, the transformation of CFC-11 also occurred, but was not accompanied with methane production, as it was the case in the suldge microcosms. Moreover, the presence of acetate, lactate and butyrate in the microcosms containing CFC-11 suggested that methanogens were inhibited in the presence of CFC-11. CFC-113 was transformed in the same way as in the microcosms inoculated with the sludge; however, the produced CTFE was further transformed to trifluoroethene (TFE). Production of HCFC-151b from HCFC-141b was also observed. In the column filled with aquifer material, only the transformations of CFC-11 and CFC-113 were observed, which is probably due to the short residence time in the column (~10 days), during which the transformation of the other compounds was not sufficiently pronounced. The increasingly reducing conditions in the column were accompanied with an increase of the degradation rates of CFC-11 and CFC-113, with a maximum reached in presence of methanogenesis. The addition of sulfate in the artificial groundwater decreased the biodegradation rates of the two compounds, and the concentration of their transformation products was simultaneously increased. This suggests that these products become more persistent under sulfate-reducing conditions. Natural attenuation designates all the processes leading to the decrease of the concentration of organic compounds migrating from a pollution source throughout a natural environment. Whereas natural attenuation or enhanced natural attenuation seem adequate for several classes of compounds, the absence of defluorination reaction of CFCs and HCFCs reported in this work suggests the use of other remediation techniques for the decontamination of sites polluted with these compounds. Indeed, the transformation products of CFCs and HCFCs still contain a fluorine atom and are not less harmfull to the environment than the parent compounds. In addition, the use of CFCs as age-dating tracers in groundwater is not recommended under anoxic conditions, as it was demonstrated here that they are not stable in such environments. The HCFCs on the other hand seem to be more persistent, and it is primordial to decrease rapidly their production and release in the environment.

EPFL2004

Alluvionnement des retenues par courants de turbidité

Giovanni De Cesare

Reservoir sedimentation by turbidity currents All lakes created on natural rivers are subjected to reservoir sedimentation. The construction of a dam significantly modifies the flow conditions of natural streams inside and downstream of an artificial lake. Considering the sediment concentration, often high during the flood season, the entering flow shows a greater density than the ambient fluid. Suspended load can therefore be entrained along the reservoir bottom all the way down to the dam in the form of turbidity currents. Research was undertaken to better understand the physical phenomena that contribute to reservoir sedimentation. The study of turbidity currents at the bottom of a lake is based on a review of the relevant literature, on measurements of water and sediment motion on site, on physical modelling of turbidity currents and on numerical flow simulation. The two-year on site investigation in the test site of Luzzone in southern Switzerland showed the relationship between precipitation, water and sediment flow and turbidity current in the reservoir even for minor events. A simple relationship describing the inflow hydrograph and the sediment transport for small floods in the incoming river was established as a set of non-dimensional equations. These relations were implemented in the numerical flow code as an upstream boundary condition. No significant occurrence of high water was observed. It was therefore impossible to establish the necessary elements for extrapolation to important flood events with their implication for the reservoir sedimentation process. The laboratory investigation confirmed the results from numerical simulation of turbidity currents. The progressing flow proceeded as predicted by theory and numerical simulation. The numerical model developed is based on the general Navier-Stokes solver code CFX-F3D from Computational Fluid Dynamics Services. User defined sediment deposition and erosion modules were added in order to take into account sedimentation and the interactions between the turbidity current and the bottom of the reservoir. The flow in the physical model as well as in the real reservoir geometry was simulated with exactly the same boundary conditions. Comparison between computer simulation, physical model and on site measurement results showed a satisfactory agreement. The code was then used to simulate turbidity currents in two dimensions in a simplified reservoir geometry with all available flow - sediment interaction models for three different particle sizes. The results were compared to data from an existing 2Dflow simulation programme and they agreed well. The study of a thousand-year flood in the Luzzone reservoir using the developed computer model revealed the potential of such a tool. In particular, the impact on the sediment deposits was analysed. A Rapid evaluation of the incidence of such an extreme turbidity flow was made. Through this study, considerable knowledge has been acquired. It can be used to formulate proposals in order to allow limited transit of sediments through the lake during floods to evacuate them directly downstream of the dam. This operation has to take place during flood periods, when the upstream and downstream reaches carry enough water. The bottom outlet therefore participates partially in the sediment evacuation at the moment of their major occurrence during floods. Another advantage of this procedure would be the reduced impact on wildlife and vegetation in the downstream river.

EPFL1998

Deposition of sediment mixture due to jet effluent into a rectangular shallow reservoir

Sameh Ahmad Kantoush, Anton Schleiss

Shallow reservoirs are threatened by fast filling up with sediments, even if the entering sediments are only suspended loads. The sedimentation process is strongly influenced by the geometry of such shallow reservoirs. In the framework of a research project, the influence of the geometry of the reservoir on sediment transport and deposition is studied by experimental approach. The experimental tests have been conducted in a 6 m long, and 4 m wide and 0.3 m deep a rectangular shallow basin. Two test procedures were examined. Crushed walnut shells with a median grain size, d50, of 50 μm, and a density of 1500 kg/m3 were used to simulate the suspended sediments. The flow and sediment conditions used during the tests grantee fully developed turbulent flow. During the tests several parameters were measured, as 2D surface velocities, 3D velocity profiles, thickness of deposited sediments, and sediment concentration at the inflow and outflow. The results help to understand the mechanism of the flow and the sediment exchange process. First, the results of a series of experimental tests with clear water and with sediments are depicted. They reveal that, under clearly identified hydraulic and geometrical conditions, the flow pattern is found to become asymmetric, in spite of the symmetrical inflow conditions, outflow conditions and geometry of the basin. But after changing the condition by adding suspended sediment to water in the mixing tank the flow pattern changed and bed forms emerged. They indicate that the flow pattern can easily switch to different directions, depending on the boundary and initial conditions. Moreover, bed forms affect the flow structure. It confirms the important role of boundary conditions in sedimentation and flow field patterns. Furthermore, these first results allow assessing the time evolution of deposition patterns.